Magnetic exchange coupled core-shell nanomagnets

ABSTRACT

A permanent magnet is fabricated such that it has a magnetically hard core surrounded by a thin magnetically soft shell. The magnetically hard core provides a relatively high intrinsic coercivity (H ci ), and the magnetically soft shell provides a relatively high magnetic flux density (B). Due to magnetic exchange coupling between the core and shell, a relatively high maximum energy product (BH) max  is achievable over a wide temperature range, including temperatures above 150° C. Further, such effects can be achieved without using rare-earth metals or precious metals helping to keep the manufacturing costs of the magnet low. To allow sufficient exchange magnetic coupling between the core and shell, the width of the shell is less than about 40 nanometers, and the overall dimensions are controlled such that the width of the shell is less than two times the Bloch domain wall thickness of the core.

CROSS REFERENCE TO RELATED APPLICATION

This application is a continuation of and claims priority to U.S. patent application Ser. No. 13/885,371, entitled “Magnetic Exchange Coupled Core-Shell Nanomagnets” and filed on May 14, 2013, which is incorporated herein by reference. U.S. patent application Ser. No. 13/885,371 claims priority to International Application No. PCT/US11/60879, entitled “Magnetic Exchange Coupled Core-Shell Nanomagnets” and having an international filing date of Nov. 15, 2011, which is incorporated herein by reference. International Application No. PCT/US11/60879 claims priority to U.S. Provisional Patent Application No. 61/413,869, entitled “Magnetic Exchange Coupled Core-Shell Nanomagnets” and filed on Nov. 15, 2010, which is incorporated herein by reference.

RELATED ART

Permanent magnets are currently used in a variety of applications, including electric motor applications, such as electric vehicles and windmill generators. Unfortunately, the performance of many permanent magnets degrades at high temperature making them unsuitable in some applications, such as electric motor applications where temperatures often exceed 150° Celsius (C). Further, many permanent magnets have expensive materials, such as precious metals or rare-earth metals, which has limited availability.

As an example, several rare-earth magnets, including Nd₂Fe₁₄B, Dy-doped Nd₂Fe₁₄B, SmCo, and Sm₂Fe₁₇N₃, have been used or considered for motors of hybrid and electric vehicles. Of such magnets, Nd₂Fe₁₄B generally provides the highest maximum energy product (BH)_(max). However, the operation temperature of this magnet is limited to around 150° C., which is attributed to a low Curie temperature of around 310 to 400° C. Furthermore, magnetization decreases with temperature and generally disappears at about the Curie temperature. To increase the operation temperature, Dy can be added, but this addition increases coercivity and decreases magnetization. Therefore, the substitution effect is relatively insignificant.

Thus, a heretofore unaddressed need exists in the art for inexpensive permanent magnets capable of efficiently operating at high temperature.

BRIEF DESCRIPTION OF THE DRAWINGS

The disclosure can be better understood with reference to the following drawings. The elements of the drawings are not necessarily to scale relative to each other, emphasis instead being placed upon clearly illustrating the principles of the disclosure. Furthermore, like reference numerals designate corresponding parts throughout the several views.

FIG. 1 depicts an exemplary embodiment of a nanomagnet particle having a magnetically hard core surrounded by a magnetically soft shell.

FIG. 2 is a plot of maximum energy product (BH_(max)) for a nanomagnet particle having a magnetically hard core (MnAl) surrounded by a magnetically soft shell (permalloy).

FIG. 3 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (τ-MnAl) surrounded by a magnetically soft shell at 300 Kelvin (K) where M_(r)/M_(s)=1 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

FIG. 4 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (τ-MnAl) surrounded by a magnetically soft shell at 300 Kelvin (K) where M_(r)/M_(s)=0.7 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

FIG. 5 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (τ-MnAl) surrounded by a magnetically soft shell at 450 Kelvin (K) where M_(r)/M_(s)=1 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

FIG. 6 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (τ-MnAl) surrounded by a magnetically soft shell at 450 Kelvin (K) where M_(r)/M_(s)=0.7 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

FIG. 7 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (MnBi) surrounded by a magnetically soft shell at 300 K where M_(r)/M_(s)=1 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

FIG. 8 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (MnBi) surrounded by a magnetically soft shell at 450 K where M_(r)/M_(s)=1 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

FIG. 9 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (BaM) surrounded by a magnetically soft shell at 300 K where M_(r)/M_(s)=1 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

FIG. 10 is a plot of volume fraction (f_(h)) of hard magnetic phase dependent (BH)_(max) for a nanomagnet particle having a magnetically hard core (BaM) surrounded by a magnetically soft shell at 450 K where M_(r)/M_(s)=1 and saturation magnetization of soft shell is in the range of 1.3 to 2.2 T.

DETAILED DESCRIPTION

The present disclosure generally pertains to magnetic exchange coupled core-shell nanomagnets. In one exemplary embodiment, a permanent magnet is fabricated such that it has a magnetically hard core surrounded by a thin magnetically soft shell. The magnetically hard core provides a relatively high intrinsic coercivity (H_(ci)), and the magnetically soft shell provides a relatively high magnetic flux density (B). Due to magnetic exchange coupling between the core and shell, a relatively high maximum energy product (BH)_(max) is achievable over a wide temperature range, including temperatures above 150° C. Further, such effects can be achieved without using rare-earth metals or precious metals helping to keep the manufacturing costs of the magnet low. To allow sufficient exchange magnetic coupling between the core and shell, the overall shell thickness is controlled such that the width of the shell is less than two times the Bloch domain wall thickness of the core.

FIG. 1 depicts an exemplary core-shell nanomagnet particle 12 manufactured to have a core 14 composed of magnetically hard material and a shell 15 composed of a magnetically soft material. In one exemplary embodiment, the material of the core 14 includes Mn, Al, Bi, Sr, Pb, Fe, or O (with at least one hard magnetic element though more preferably with at least two hard magnetic elements), and the material of the shell includes Fe, Co, Ni, Al, Si, N, or O (with at least one soft magnetic element though more preferably with at least two soft magnetic elements). As an example, the magnetically hard core 14 may be composed of MnAl or M-type hexaferrite (BaFe₁₂O₁₉) or MnBi, and the magnetically soft shell 15 may be composed of Fe₆₅Co₃₅, Permalloy (Fe₂₀Ni₈₀), or Sendust (FeAlSi). However, in other embodiments, other elements and/or combination of elements are possible.

The shape of the core-shell particle 12, as well as the core 14, is generally spherical, though it can have other shapes, such as needlelike or hexagonal, in other embodiments. Further, the shell 15 forms a hollow sphere that encompasses and surrounds the core 14, and the core 14 fills the void within the hollow sphere. In other embodiments, other shapes of the shell 15, such as cylinder, cube, or hexagon, are possible. In one exemplary embodiment, the thickness of the shell 15 (δ_(s)) is between about 20 nm and 40 nm, and such thickness is less than two times the Bloch domain wall thickness of the core 14. Further, the thickness of the shell 15 is uniform around the core 14. However, it should be emphasized that other shapes and configurations of the core-shell particle 12 are possible in other embodiments.

The (BH)_(max) for the core-shell particle 12 can be characterized by the following formulas (assuming that M_(r)=M_(s)).

$\begin{matrix} {M_{r} = {{{f_{h}M_{h}} + {f_{s}M_{s}\mspace{14mu}{when}\mspace{14mu} M_{s}}} = \left. M_{r}\rightarrow\begin{matrix} {{{Eq}.\mspace{11mu}(6)},{R.\mspace{11mu}{Skomski}}} \\ {{P.\mspace{11mu} 3591.}\mspace{11mu}{E.\mspace{11mu}{Kneller}}} \end{matrix} \right.}} & (1) \\ {{{\mu_{0}H_{N}} = \left. {2\frac{{f_{s}K_{s}} + {f_{h}K_{h}}}{{f_{s}M_{s}} + {f_{h}M_{h}}}}\rightarrow{{Eq}.\mspace{11mu}(8)} \right.},{R.\mspace{11mu}{Skomiski}}} & (2) \\ {{\left. \begin{matrix} {({BH})_{\max} = {{\frac{\mu_{0}M_{r}^{2}}{4}\mspace{14mu}{for}\mspace{14mu} H_{N}} > \frac{M_{r}}{2}}} \\ {({BH})_{\max} = {{\frac{\mu_{0}H_{N}M_{r}}{2}\mspace{14mu}{for}\mspace{14mu} H_{N}} < \frac{M_{r}}{2}}} \end{matrix} \right\}\begin{matrix} {{p.\mspace{11mu} 15814},{R.\mspace{11mu}{Skomski}}} \\ {{P.\mspace{11mu} 3588},{E.\mspace{11mu}{Kneller}}} \end{matrix}}{{M_{r}\text{:}\mspace{11mu}{Remanence}\mspace{14mu}{of}\mspace{14mu}{hard}} + {{soft}\mspace{14mu}{phases}}}{M_{s}\text{:}\mspace{11mu}{Saturation}\mspace{14mu}{magnetization}\mspace{14mu}{of}\mspace{14mu}{soft}\mspace{14mu}{magnetic}\mspace{14mu}{phase}}{M_{h}\text{:}\mspace{11mu}{Saturation}\mspace{14mu}{magnetization}\mspace{14mu}{of}\mspace{14mu}{hard}\mspace{14mu}{magnetic}\mspace{14mu}{phase}}{K_{h}\text{:}\mspace{11mu}{Magnetic}\mspace{14mu}{anisotrophy}\mspace{14mu}{energy}\mspace{14mu}{of}\mspace{14mu}{hard}\mspace{14mu}{magnetic}\mspace{14mu}{phase}}{K_{s}\text{:}\mspace{11mu}{Magnetic}\mspace{14mu}{anisotrophy}\mspace{14mu}{energy}\mspace{14mu}{of}\mspace{14mu}{soft}\mspace{14mu}{magnetic}\mspace{14mu}{phase}}{f_{h}\;\text{:}\mspace{11mu}{Volume}\mspace{14mu}{fraction}\mspace{14mu}{of}\mspace{14mu}{hard}\mspace{14mu}{magnetic}\mspace{14mu}{phase}}{f_{s}\text{:}\mspace{14mu}{Volume}\mspace{14mu}{fraction}\mspace{14mu}{of}\mspace{14mu}{soft}\mspace{14mu}{magnetic}\mspace{14mu}{phase}}{\mu_{0}\text{:}\mspace{11mu} 4\pi \times 10^{- 7}N\text{/}A^{2}}} & \begin{matrix} (3) \\ (4) \end{matrix} \end{matrix}$

-   [Ref1] R Skomski, and J. M D Coey, “Giant energy product in     nanostructured two-phase magnets”, Phys. Rev. B. 48, 21 (1993) -   [Ref2] E. F. Kneller, and R. Hawig, “The exchange-spring magnet: A     new material principle for permanent magnets”, IEEE Trans. Magn. 27,     pp 3588-3600, (1991)

$\begin{matrix} {{{{Assuming}\mspace{14mu} M_{r}} = {0.7\mspace{11mu} M_{s}}},{B_{r} = {\mu_{0}M_{r}}},{Therefore},{B_{r} = {0.7\mspace{14mu}\mu_{0}M_{s}}},{B_{r} = {0.7B_{s}}}} & \; \\ {{M_{r} = {\frac{{f_{h}B_{r\_ hard}} + {f_{s}B_{r\_ soft}}}{\mu_{0}} = {{\frac{{f_{h}B_{r\_ hard}} + {\left( {1 - f_{h}} \right)B_{r\_ soft}}}{\mu_{0}}\left\lbrack {A\text{/}m} \right\rbrack} = {\frac{0.7\left\lbrack {B_{s\_ soft} - {f_{h}\left( {B_{s\_ soft} - B_{s\_ hard}} \right)}} \right\rbrack}{\mu_{0}}\left\lbrack {A\text{/}m} \right\rbrack}}}}{{{For}\mspace{14mu} H_{N}} > \frac{M_{r}}{2}}} & (5) \\ {({BH})_{\max} = {\frac{\mu_{0}M_{r}^{2}}{4} = {{\frac{\mu_{0}\left\{ \frac{0.7\left\lbrack {B_{s\_ soft} - {f_{h}\left( {B_{s\_ soft} - B_{s\_ hard}} \right)}} \right\rbrack}{\mu_{0}} \right\}^{2}}{4}\left\lbrack {\frac{N}{A^{2}}\frac{A^{2}}{m^{2}}} \right\rbrack} = {\quad{\left\lbrack {\frac{N}{A \cdot m}\frac{A}{m}} \right\rbrack = {\left\lbrack {{T \cdot A}\text{/}m} \right\rbrack = {\frac{0.49{\pi\left\lbrack {B_{s\_ soft} - {f_{h}\left( {B_{s\_ soft} - B_{s\_ hard}} \right)}} \right\rbrack}^{2}}{10^{5} \times \mu_{0}} = {{{\frac{4.9{\pi\left\lbrack {B_{s\_ soft} - {f_{h}\left( {B_{s\_ soft} - B_{s\_ hard}} \right)}} \right\rbrack}^{2}}{10^{6} \times \mu_{0}}\left\lbrack {{MG} \cdot {Oe}} \right\rbrack}{For}\mspace{14mu} H_{N}} < \frac{M_{r}}{2}}}}}\mspace{31mu}}}}} & (6) \\ {{({BH})_{\max} = {\frac{\mu_{0}H_{N}M_{r}}{2} = {\frac{2\left( \frac{{f_{s}K_{s}} + {f_{h}K_{h}}}{{f_{s}M_{s}} + {f_{h}M_{h}}} \right)\left( {{f_{s}M_{s}} + {f_{h}M_{h}}} \right)}{2} = {{{f_{s}K_{s}} + {f_{h}K_{h}}} = {{{\left( {1 - f_{h}} \right)K_{s}} + {f_{h}K_{h}}} = {{K_{s} + {f_{h}\left( {K_{h} - K_{s}} \right)}} = {{{\frac{4{\pi\left\lbrack {K_{s} + {f_{h}\left( {K_{h} - K_{s}} \right)}} \right\rbrack}}{10^{5}}\left\lbrack {{MG} \cdot {Oe}} \right\rbrack}\left\lbrack \frac{J}{m^{3}} \right\rbrack} = {\left\lbrack \frac{{kg} \cdot m^{2}}{\sec^{2}m^{3}} \right\rbrack = {\left\lbrack {\frac{kg}{\sec^{2}m}\frac{A}{A}} \right\rbrack = {\left\lbrack {\frac{kg}{\sec^{2}A}\frac{A}{m}} \right\rbrack = {\left\lbrack {T\frac{A}{m}} \right\rbrack = \left\lbrack \frac{N}{m^{2}} \right\rbrack}}}}}}}}}}}{B_{s\_ soft}\text{:}\mspace{11mu} B_{s}\mspace{14mu}{of}\mspace{14mu}{soft}\mspace{14mu}{magnetic}\mspace{14mu}{{phase}\mspace{14mu}\lbrack T\rbrack}}{B_{h\_ hard}\text{:}\mspace{11mu} B_{s}\mspace{14mu}{of}\mspace{14mu}{hard}\mspace{14mu}{magnetic}\mspace{14mu}{{phase}\mspace{14mu}\lbrack T\rbrack}}} & (7) \end{matrix}$

FIG. 2 shows (BH)_(max) of a τ-phase MnAl-permalloy core-shell nanomagnet in terms of volume fraction of hard core (f_(h)). The hard magnetic τ-MnAl core (saturation magnetization=0.7 T; magnetic anisotropy constant K_(h)=1 MJ/m³) and soft magnetic permalloy shell (saturation magnetization=1 T; magnetic anisotropy constant K_(s)=0.01 MJ/m³) were used.

Equations (6) and (7) were used to calculate (BH)_(max) of MnAl-permalloy core-shell nanomagnet for H_(n)>M_(r)/2 and H_(n)<M_(r)/2, respectively. It is noted that (BH)_(max) is about 12 MGOe at H_(n)=M_(r)/2 and f_(h)=8%, while (BH)_(max) of pure (f_(h)=100%) MnAl nanomagnet is about 7 MGOe.

A τ-phase MnAl core-soft shell nanomagnet (i.e., a nanomagnet having τ-phase MnAl forming the hard magnetic core 14) where the shell 15 is composed of a soft magnetic alloy was used to calculate (BH)_(max) in terms of saturation magnetization (M_(s)) and shell thickness (δ_(s)) using equations (6) and (7). However, it is generally desirable for the shell thickness (δ_(s)) to be smaller than about 2 times the Bloch domain wall thickness of the core 14 to allow efficient exchange magnetic coupling between the core 14 and shell 15. This is because the exchange magnetic coupling becomes weaker as the shell thickness increases over the Bloch domain wall thickness. The Bloch domain wall thickness for τ-phase MnAl is about 15 nm [G. G. Korznikova, J. of Microscopy, Vol. 239, 239, 2010]. Therefore, shell thickness is preferably thinner than 30 nm. FIG. 3 shows the (BH)_(max) of MnAl—CoFe (2.2 T) core-shell nanomagnet becomes about 55 MGOe when exchange coupling exists. This high (BH)_(max) is attributable to the exchange coupling.

In another embodiment, a barium ferrite (BaM: BaFe₁₂O₁₉)—Fe₆₅Co₃₅ core-shell nanomagnet was used to calculate (BH)_(max). FIG. 9 shows (BH)_(max) of such nanomagnet as a function of volume fraction (f_(h)) of hard BaM core. The (BH)_(max) was estimated to be about 22.5 MGOe for f_(h) equal to 55%. About 11 nm thick shell for 100 nm barium ferrite particle is desired to provide approximately 22.5 MGOe as the Bloch domain wall thickness for barium ferrite is about 14 nm [M. Ziese and M. J. Thornton, Spin Electronics, p. 220, Spring 2001].

FIGS. 4-10 depict estimate of (BH)_(max) for various core-shell nanomagnets for different temperatures. In particular, FIG. 3 depicts a plot of (BH)_(max) at 300 K using τ-MnAl for the core 14 where M_(r)/M_(s)=1, and FIG. 4 depicts a plot of (BH)_(max) at 300 K using τ-MnAl for the core 14 where M_(r)/M_(s)=0.7. FIG. 5 depicts a plot of (BH)_(max) at 450 K using τ-MnAl for the core 14 where M_(r)/M_(s)=1, and FIG. 6 depicts a plot of (BH)_(max) at 450 K using τ-MnAl for the core 14 where M_(r)/M_(s)=0.7. FIG. 7 depicts a plot of (BH)_(max) at 300 K using MnBi for the core 14 where M_(r)/M_(s)=1, and FIG. 8 depicts a plot of (BH)_(max) at 450 K using MnBi for the core 14 where M_(r)/M_(s)=1. Further, FIG. 9 depicts a plot of (BH)_(max) at 300 K using BaM for the core 14 where M_(r)/M_(s)=1, and FIG. 10 depicts a plot of (BH)_(max) BaM at 450 K using for the core 14 where M_(r)/M_(s)=1.

Note that there are various techniques that could be used to fabricate a nanomagnet, as described herein, including electroless plating, chemical and physical synthesis, and embedding core-shell nanomagnets in a polymeric matrix.

In one exemplary embodiment, M-type hexaferrite nanoparticles and anionic surfactant are mixed in distilled water, while mechanically stirring with argon gas purging and then washed with deionized water. The anionic surfactant allows Fe²⁺ and Co²⁺ cations to adhere to the core hexaferrite particles. When the anionic surfactant is dispersed in water, the hydrophilic head is likely to face to water, while the hydrophobic tail avoids water. The choice of the anionic surfactant could be sodium dodecyl sulfate (SDS), sodium laurilsulfate or sodium lauryl sulfate (SLS), though other anionic surfactants are possible. Aqueous solutions of SDS have been conventionally used for dispersing (or suspending) magnetite (Fe₃O₄) particles. Note that the M-type hexaferrite core particle is already an oxide. Therefore, the hexaferrite is chemically stable, but not Fe and Co. Prior to adding FeCl₂·4H₂O and CoCl₂·6H₂O precursory shell materials to the solution, the anionic surfactant containing solution may be deaerated by purging with Ar gas. The purging preferably continues until the end of the coating process. Reduction agent NdBH₄ is dropped into the solution at a desired flow rate, and transition metal ions are thereby brought to their metallic state. The Co—Fe coated M-type hexaferrites is filtered and dried in an oven at about 80° C. This same process is also applicable to manufacturing of MnAl and MnBi core-shell nanoparticles under an inert atmosphere. In other embodiments, other techniques can be used for fabricating nanomagnet particles. 

Now, therefore, the following is claimed:
 1. A core-shell nanoparticle comprising: a core of hard magnetic material; and a shell of soft magnetic material encasing the core, wherein a thickness of the shell is less than 40 nanometers and less than two times a Bloch domain wall thickness of the core.
 2. The core-shell nanoparticle of claim 1, wherein the shell has a uniform thickness around the core.
 3. The core-shell nanoparticle of claim 1, wherein the core has a diameter greater than 50 nanometers.
 4. The core-shell nanoparticle of claim 2, wherein the core has a diameter less than 250 nanometers.
 5. The core-shell nanoparticle of claim 1, wherein material of the core includes at least one of the group including: Mn, Al, Bi, Sr, Pb, Fe, and O.
 6. The core-shell nanoparticle of claim 1, wherein material of the core includes at least one of the group including: MnAl, BaFe₁₂O₁₉, and MnBi.
 7. The core-shell nanoparticle of claim 1, wherein material of the core has an M_(h) greater than 0.6 tesla.
 8. The core-shell nanoparticle of claim 1, wherein material of the shell includes at least one of the group including: Fe, Co, Ni, Al, Si, N, and O.
 9. The core-shell nanoparticle of claim 1, wherein material of the shell includes at least one of the group including: Fe₆₅Co₃₅, Fe₂₀Ni₈₀ and FeAlSi.
 10. The core-shell nanoparticle of claim 1, wherein material of the shell has a Br between 1.3 and 2.2 tesla.
 11. The core-shell nanoparticle of claim 1, wherein the nanoparticle has a maximum energy storage, (BH)_(max), greater than 30 MGOe. 